Bis-diazo-diimino compounds



Patented Mar. 8, 1938 UNITEQ STATES BIS-DIAZO-DIIMINO COMPOUNDS Eugene A. Markush,

Jersey City, Mark S.

Mayzner, Asbury Park, and Julius Miller, Newark, N. J., assignors to Pharma Chemical Corporation, New York,

New York N. Y., acorporation of No Drawing. Application January 18, 1935, Serial No. 2,355

11 Claims.

in which R is the residue of a diazotized aromatic amine, n being 2 when R is the residue of a diazotized aromatic amine, n being 1 when R is the residue of a tetrazotized aromatic amine, X--X is the residue of an aliphatic diimino compound containing a water-solubilizing group and which may contain halogen, hydroxy, nitro, alkyl, aralkyl, and aryl substitutions, the N=N groups being combined with the imino groups of the aliphatic diimino compound.

We designate these products as aliphatic bis- (diazo-imino) compounds.

These products when mixed with coupling components produce stable compositions which yield valuable dyes in substance, as well as in dyeing and printing processes.

We give the following as examples of our invention Example 1 158 parts (by weight) 4-ch1or-2-amino-anisol are dissolved in 400 parts water and 270 parts hydrochloric acid 20 B. The solution is cooled with ice and diazotized in the usual manner with '70 parts sodium nitrite dissolved in 280 parts of Water.

97 parts ethylene-diimine-diacetic acid, or ethylene-bis-(imino-acetic acid) are dissolved in about 1000 parts water containing 200' parts of sodium carbonate, cooled to 8-10 C. and the solution of the above diazonium is added slowly.

When about one third of the diazonium has 60 stable to alkalies and in presence of acids easily splits to reform the l-chlor-Z-diazo-anisole and ethylene-diimino-diacetic acid. Its probable formula is:

(IJOONa oooNa om-o- (3H1 O-GHa N=NNoHT-cH,-N =N Example 2 142 parts l-chlor-Z-amino-toluol are diazotized in the well known manner with hydrochloric acid and sodium nitrite. The clear diazonium solution is added slowly with good stirring to a solution of 151 parts ethylene-bis-(imino-iso-butyric acid) di-sodium salt Berichte (44, 1135 (1911)) in 1000 parts water and 200 parts sodium carbonate.

The whole is kept at 10 C. When all diazonium has been introduced and complete condensation effected, the precipitated bis-(diazoimino) body is filtered, pressed and dried. A brownish powder is obtained with a yield of 370 parts. It is well soluble in water, stable to drying, grinding and heat and on treatment with acids is reconverted into -chlor-Z-diazo-toluol and ethylene-bis-(imino-iso-butyric acid). Its formula is in all probability:-

Cl CH3 CHa C1 C0 ONa CO ONa Eazample 3 In a similar manner, the diazonium of 185 parts ortho-amino-diphenyl-ether is condensed with 155 parts of the disodium salt of pentamethylene bis (alpha imino propionic acid) (Berichte 47, 2413 (1914) The bis-(diazo-imino) compound is isolated by the addition of salt, filtered, pressed and dried. The cream colored compound shows similar properties to the above mentioned compounds. Its probable formula is:

l CH3 N=NIIT-CH- C O O Na (3H2 r (I111: CH2

' CH2 CH3 a water at 40 C.

' Example 4 d 122 parts of dianisidine are pasted in 200 parts '130 parts of 720 B. hydro-4 chloric acid are added and the whole stirred at C., until complete solution has been reached.

Sufiicient ice is added tolcool to'O" .C.,1'and '1404 parts additional hydrochloric acid arewadded, foli lowed immediately by a solution of 70 parts of sodium nitrite in 300 parts of water. I The resultingrclear tetra'zo solutionis entered slowly into a 5 C., solution of 125 parts ethylene-bis-(iminoa' parts of water acetic acid) disodium salt in 1000 and 250 parts soda ash;

The addition should take at least one hour. 7 When all is in, stirring is continued for 24 hours and the temperature never allowed to'rise above 8 C.

- 'The solution is then saturated with solid salt" and heated very slowly to 70'-75 C. ;A yellow precipitate appears. 7 perature and filter, press and dry; The yield is V 430 .parts. 1

'ethylene-bis- (imino-acetic-acid) formula is 2 V Allow to cool to room tem- 2 r I 7 1 a 110,276

The'eb'r'npouncl is a yellowish crystallin powder, ,extremely soluble inwater. Upon treating with acids. it regeneratesftetrazo-dianisidine and CHaO y The followingchart illustrates some of the various bis-(diazo-imino) compounds prepared by us. The scope of our invention is not limited to these mentioned. 'Ih'ey'are prepared in; the

Its probable manner described in the above mentioned exe" Amine (liazotizcd' I Stabilizer Probable formula Trimetbylene-bis-(iininoa (l) Benzidinem; l a aceticac dy :Trimethylene-bis- (imino- :acetic ac d). V 1

Pentamethylene bisa Dianisidin (imino-acetic acid).

Trimethylene-bis-(iminoiso-butyric acid);

' V Berichte58, 1879 (1925) 4' haethyl-iamine diphenylether a OCH OCH

I H: 7 (EH: OH:

I H: CH:

Stabilizer Probable formula Amine diazotized (5) CH2, Penta-methylene-bis-(imi- CH3 no-propionic acid) I /OH:

NH: Berichte 47, 2413 N=N1TIGHOOOH CH: 1 E C 0 CH2 4-benzoy1ami11o-2-amino toluol 1 CH3 CH2 4-amin0-2-benzoylamino-toluene Meta. chloroaniline CHa (IJOHa benzol 2-5 dichloroaniline 2,3 diphenyl piperazinbis-(2,3 diearboxylic acid).

Beriehte 47, 2409 EthyIene-bis-(imino-acetic acid) Ethylene-bis-(imino-diacetic acid).

Trimethylene-bis- (iminophenyl-acetic acid).

Berichte 58, 1880 (1925) COOH Amine diazotized V Stabilizer V Probable formula X10 NH, V Trimethylene bis-(imino- CH; I] I 7 propionic acid), 7

l C r N=N-N-OH:COOH

10 V V 7 V I V C EH1 v I 7 u In w Alphn-amino-unthraquinona H 0 (EH: I (l? V V V O i on, H,

v I 000E OOH 75 invention; 7 i

(14) 1-methoxye2-amiuo-4-clilor- Methylenebis-(im ino,

V benzol. V 'acetic'acid). V 7

ooHi r oom om H nn-om-ooon 7 NH, N=N--NCHz- N-N=N CH1 r NH-CH2-COOH V r V v t c0011 COOH 01 .01 r 01 (15) 1 methyl 2amin0 4 chlot- Methylene-bis-(imino-ace} benzene. v tic acid) 1 V (IE3 Y '1 on, r 1 on, NH-CIh-COOH I 7 NH: 7 v N=N-NQH:N N=N- V CH1 q H, 7 0H, 7

NH-CHz-COOH Y V 7 0011 oooH V 01 7 I T 01 V 7 C1 7 '70 In the following we recordadditional arni-nes 'I'he mechanics of the reaction in each case are; 7

and diimino compounds applied in support ofiour alike and identical with those specified in the examples with only minor changes or adjustments;

/ Methylene-bis-(imino-isobutyrlc acid) Methylene-bis-(iminNphenyl-methyl acetic-acid) NH-- O O OH CgHg NEE-II G O H Methylene-bis-(imino-phenyLacetic acid) C6115 ITIH-JlH-COOH E NIL-CH-CO OlI Methylene-bis-(imino-bis-diphenyl-acetic-acid) NH-C-C 0 0H oHs N H-C-C O OH These diimines are characterized by the general formula:

where X represents the aliphatic chain and Y an aldehyde or'ketone residue whichmay be substituted and such substitutions may be a sulphonic groupas well Formation of dyes I Example I 95 parts *of disodium salt ofbis-4' ch1oro-1- methoxy-2diazoethylene-bis-(imino acetic acid) are mixed with llO parts of, aceto-acet-alphanaphthylamid. The resulting greyish white powder is stable to storage. It'is veryi readily soluble in water with the suitable addition of alkali.

Upon treatment with organic acids the solution.

of this mixture readily yieldsa clear greenish yellow pigment.

The iollowingchart illustrates various compo-.

sitions and resultant shades of the azo dyes obtainable from each. The amounts of each component in the mixtur'e'are approximately molecular.

Bis-(diam imino) Coupling compounds components shades See chart formula (4) Beta hydroxy naph- Red.

ghoic acid o toluil See chart formula (6)-..." Beta hydroxy -naph- Orange;

' thoic-acid-anilid. See chart formula (3) Beta hydroxy naph- Blue.

' thoic-acid-anilid. See chart formula (ll) Beta -hydroxy naph- Reddish blue.

. thoic-acid-anilide. See chart formula (11) Beta hydroxy naph- Greenish blue.

tlhgic acid o toluil See chart formula (8) Beta hydroxy naph- Bordeaux.

1 r V v thgic acid o anisi- See chart formula (5) Beta hydroxynaph- Blueish red.

' V tihgic acid 0 anisil See chart formula (9) Diacet0-acet-toluidid Yellow. See chart formula (9) Phenyl -methyl-pyra- Reddlsh yelzolon. low. See chart formula (7) Beta hydroxy-naph- Scarlet.

thoic acid m xyli- See chart formula (4) 2 hydroxy carbazol Brown.

. o garboxy o anisi- See chart formula (1) Diacto-zicet-benzidid- Yellowish orange.

The following coupling components may also be employed: 7

Aceto-acetyl-alpha-naphthylamine, Aceto-acetyl-beta-naphthylamine, 2'3hydroxynaphthoic' acid-2-naphthylamide, 2'3'-hydroxynaphthoic aczid-S-chloranilide, V 2'3'-hydroxynaphthoic acid-5-chloro-2-anis1- dide, a

2' 3-hydroxynaphthoic acid-3-nitranilide, 2'3'-hydroxynaphthoic" acid-3-nitranilide," 2.3-hydroxynaphthoyl ortho-chloraniline, 2.3-hydroxynaphthoyl-meta-toluidine, 2.3-hydroxynaphthoyl-5-chloro-1.2-anisidine, 2.3-hydroxylnaphthoyl-dianisidine, Alpha-hydroxyrnaphthoecarbazole carboxylic acid-S-nitro-o-anisidine,

Alpha-hydroxy-naphtho-carbazole carboxylic acid-xylidine.

For the preparation ot the dyestufl' in substance, 20 parts of themixture are dissolved in 150 parts water and 6'parts sodium hydroxide 32 B. If necessary a minimum quantity of a suitable solvent such as alcohol or glycol ether is added to assist the solubility. The solution is acidified in excess with formic acid or acetic acid and heated until maximum formation of the dyestuif occurs. 7

Suitable substrata maybe used if desired. The pigment is filtered, dried and ground. V

The most important use of these compositions is for the application of colors in dyeing and printing of textile fibres.

The following method of application will illustrate the procedure: J

1 mol. of the 'bis-(diazo-imino) compound is mixed with 2 mols of a coupling component. Then 2 parts of this mixtureare dissolved in 7 parts water, 7 q r part para soap, 1 parts caustic soda solution 30 B., 2 parts cellosolve or denatured alcohol and the resulting solution thickened to a paste with 15 parts starchgum tragacanth.

This paste is printed on the cotton cloth and hung up to dry. The printed cloth may be developed immediately after drying, or the dried printed cloth stored until required by the printer. The developing is done by placing the cloth in an ager and steaming in the presence of acetic, formic or other organic acid vapor for five minutes. It is then soaped hot, rinsed well and dried.

Where the use of an ager is inconvenient, the developing may be done by immersing the printed cloth in a warm bath of acetic, formic or other acids, or mixtures thereof, in the presence of Glaubers salt. This developing bath is heated until the shades have reached maximum fullness. Furthermore, the printed material may be padded with the acid mixture using the well known padding method after which the material is dried with heat, rinsed, soaped, washed well and dried.

The printing paste of this mixture, when printed on cotton or rayon, and developed, yields a bright clear shade of excellent fastness to light, rubbing, kier boiling and chlorine.

What we claim is:

1. As a new compound, the aliphatic diimino compound having the formula 2. As a new compound, the aliphatic diimino compound producible by combining 2 molecules of diazotized l-chlor-2-amino-anisol with 1 molecule of ethylenediimino-diacetic acid, which compound is water-soluble and which is capable of being split -up into diazo-4-chlbr-2-aminoanisol and ethylene-diimino-diacetic acid upon treatment with acid.

3. A process for the production of aliphatic diimino compounds which consists in reacting upon 1 mol. of ethylene-diiminodiacetic acid with 2 mols of diazotized 4-chlor-2-amino-anisol.

4. Diazoimino compounds having the formula Y-OH2NN=N wherein R. is the aryl radical of a diazotized aromatic amine, X is a divalent saturated aliphatic hydrocarbon radical, Y is a water solubilizing substituent selected from the group consisting of carboxyl and sulfo, and n is at least one and not more than two.

5. Diazoimino compounds having the formula wherein R represents the aryl radical of a diazotized aromatic amine, n is at least one and not more than two, and n signifies an integer.

sisting of carboxyl and sulfo.

8. Diazoimino compounds having the formula l HOOC-OHz-NN=N wherein R represents the aryl radical of a diazotized aromatic amine and n is at least one and not more than two.

9. Diazoimino compounds having the formula OCH:

C Ha

nooc oinN-N=1 r 10. Diazoimino compounds having the formula HO C-OH1-NN=NR on. HO 0 OCHzl T-N=NR" wherein each R" represents the phenyl radical of a diazotized amine of the benzene series.

11. Diazoimino compounds having the formula Ho0coH2-l I-N=NR" (3H2 ?H2 HO 0 GCH2NN=NR" wherein each R" represents the chlor-methoxyphenyl radical of a diazotized chlor-anisidine.

EUGENE A. MARKUSH.

MARK s. MAYZNER. JULIUS MILLER. 

